WO2016084924A1

WO2016084924A1 - Magnesium-containing electrolytic solution

Info

Publication number: WO2016084924A1
Application number: PCT/JP2015/083325
Authority: WO
Inventors: 和彦里; 高広清洲; 水田　浩徳; 悟郎森; 訓明岡本
Original assignee: 和光純薬工業株式会社
Priority date: 2014-11-28
Filing date: 2015-11-27
Publication date: 2016-06-02
Also published as: CN107004906A; TW201628251A; JP6575531B2; US10367231B2; TWI674692B; KR20170089890A; PL3226340T3; EP3226340A1; EP3226340B1; US20170331154A1; EP3226340A4; CN107004906B; JPWO2016084924A1

Abstract

The purpose of the present invention is to provide an electrolytic solution having a high oxidative decomposition potential, whereby dissolution and deposition of magnesium proceed repeatedly and stably, using a non-nucleophilic alkoxide-based magnesium salt. The present invention relates to: (1) an electrolytic solution for a magnesium cell, obtained by mixing a compound represented by general formula (I), a Lewis acid, and a solvent; (2) an electrochemical device including the electrolytic solution, a positive electrode, and a negative electrode; and (3) a compound represented by general formula (I').

Description

Magnesium-containing electrolyte

The present invention relates to an electrolytic solution containing magnesium ions and an electrochemical device including the electrolytic solution.

Magnesium has a large electric capacity per unit volume because the ions are multivalent ions. Magnesium has a higher melting point than lithium and is safe, and also has the advantage that the distribution of resources on the earth is small, the amount of resources is abundant, and it is inexpensive. Therefore, a magnesium ion battery using metallic magnesium as a negative electrode has attracted attention as a next-generation battery that replaces a lithium ion battery.

However, in a magnesium ion battery using metallic magnesium as a negative electrode, a passive film is formed on the electrode surface when magnesium reacts with the electrolyte due to its high reducibility. As a result, reversible dissolution and precipitation of magnesium are inhibited, and the negative electrode reaction becomes difficult.

As an electrolytic solution that does not form such a passive film, an electrolytic solution in which Grignard reagent RMGX (R is an alkyl group or an aryl group, X is chlorine or bromine) is dissolved in tetrahydrofuran is known, Reversible dissolution and precipitation of magnesium have been confirmed.

On the other hand, Aurbach et al. Prepared a THF solution of Mg (AlCl ₂ BuEt) ₂ using dibutylmagnesium Bu ₂ Mg and ethylaluminum dichloride EtAlCl ₂ and found that it can be used up to a potential of about 2.4 V with respect to magnesium. (Non-Patent Document 1).

However, electrolytes using these Grignard reagents and alkylmagnesium have nucleophilic properties, so there is a concern of direct reaction with chemically active active materials and sulfur used in the positive electrode. There were restrictions on use.

On the other hand, Wang et al. Have reported an electrolyte solution that can be used up to about 2.6 V with respect to magnesium by mixing non-nucleophilic phenoxide magnesium salt and aluminum chloride (Non-patent Document 2). .

In addition, Liao et al. Reported an electrolyte solution having an oxidation resistance of about 2.5 V against magnesium by mixing non-nucleophilic alkoxide-based magnesium salt and aluminum chloride. (Non-Patent Document 3).

The electrolytes described in Non-Patent Document 2 and Non-Patent Document 3 have reported electrolytes having a wide potential window after using a non-nucleophilic magnesium salt as described above. There is a current need for operable electrolytes.
That is, an object of the present invention is to provide an electrolytic solution that uses a non-nucleophilic alkoxide-based magnesium salt and has a high oxidative decomposition potential and allows magnesium dissolution and precipitation to proceed repeatedly and stably.

The present invention provides a magnesium battery electrolyte comprising a mixture of a compound represented by the following general formula (I), a Lewis acid and a solvent:

(In the formula, Y represents a carbon atom or a silicon atom, X represents a chlorine atom or a bromine atom, and R ₁ may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent. Represents a good aryl group having 6 to 10 carbon atoms, and R ₂ and R ₃ each independently represents: magnesium chlorideoxy group (—OMgCl); magnesium bromideoxy group (—OMgBr); alkenyl having 1 to 6 carbon atoms A group; an alkyl group having 1 to 6 carbon atoms which may have a halogeno group or an alkoxy group as a substituent; or a halogeno group, an alkyl group, a halogenoalkyl group or an alkoxy group which may have a substituent. Represents a good aryl group having 6 to 10 carbon atoms.) ”,“ An electrochemical device including the above electrolytic solution, positive electrode and negative electrode ”and“ a compound represented by the following general formula (I ′):

(In the formula, X represents a chlorine atom or a bromine atom, and R ′ ₁ is an aryl group having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent. R ′ ₂ and R ′ ₃ each independently have a hydrogen atom; —OMgCl; —OMgBr; an alkenyl group having 1 to 6 carbon atoms; a halogeno group or an alkoxy group as a substituent. An alkyl group having 1 to 6 carbon atoms; or an aryl group having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent.

Since the electrolytic solution of the present invention has a higher oxidative decomposition potential than conventional electrolytic solutions, it can be used as an electrolytic solution for high-voltage magnesium batteries. Moreover, when the electrolytic solution of the present invention is used as an electrolytic solution for a magnesium secondary battery, there is an effect that dissolution and precipitation of magnesium repeatedly and stably proceeds. Furthermore, the electrolytic solution of the present invention also has excellent storage stability.

The graph which showed the result of having carried out 10 cycles by the CV measurement using the electrolyte solution 1 [triphenylmethoxymagnesium chloride-aluminum chloride / tetrahydrofuran (THF) solution] in Example 7 is shown. The graph which showed the result of having carried out 10 cycles by the CV measurement using the electrolyte solution 2 [triphenylmethoxy magnesium chloride-aluminum chloride / triglyme solution] in Example 7 is shown. The graph which showed the result of having carried out 40 cycles by the CV measurement using the electrolyte solution 2 [triphenylmethoxy magnesium chloride-aluminum chloride / triglyme solution] in Example 7 is shown. In Comparative Example 3 represents a graph showing the results obtained by 10 cycles CV measurement using the comparative electrolytic solution _{1 [(tert-BuOMgCl) 6} -AlCl 3 / THF solution. In Comparative Example 3 represents a graph showing the results obtained by 10 cycles CV measurement using the comparative electrolytic solution _{_{2 [MgCl 2 -Me 2 AlCl-}} Bu 4 NCl / THF solution. The graph which showed the result of having carried out 10 cycles by the CV measurement using the electrolyte solution 7 [triphenylsiloxymagnesium chloride-aluminum chloride / THF solution] in Example 16 is shown. In Comparative Example 5 represents a graph showing the results obtained by 10 cycles CV measurement using the comparative electrolytic solution _{_{3 [(Me 3 SiOMgCl) 6}} -AlCl 3 / THF solution.

[Compound represented by the general formula (I)]
Y of the compound represented by the general formula (I) represents a carbon atom or a silicon atom, and a silicon atom is preferable. The compound represented by the general formula (I) in which Y is a silicon atom exhibits better storage stability than when Y is a carbon atom.

X of the compound represented by the general formula (I) represents a chlorine atom or a bromine atom, and a chlorine atom is preferable.

Examples of the aryl group having 6 to 10 carbon atoms in R ₁ to R ₃ of the compound represented by the general formula (I) include a phenyl group or a naphthyl group, and a phenyl group is preferable.

Examples of the halogeno group as the substituent of the aryl group having 6 to 10 carbon atoms in R ₁ to R ₃ include a fluoro group, a chloro group, a bromo group, and an iodo group, and a fluoro group is preferable.

The alkyl group as a substituent of the aryl group having 6 to 10 carbon atoms in R ₁ to R ₃ is usually an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and may be linear or branched. The shape may be circular or circular. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group Tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, 3-methylpentyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, cyclopentyl group, Examples thereof include a cyclohexyl group, and a methyl group, an ethyl group, an n-propyl group, and an n-butyl group are preferable, and a methyl group is more preferable.

The halogenoalkyl group as a substituent of the aryl group having 6 to 10 carbon atoms in R ₁ to R ₃ may be linear, branched or cyclic, but is preferably linear, and usually has 1 to 6 carbon atoms. It is preferably 1 to 3. Specific examples include a fluoroalkyl group, a chloroalkyl group, a bromoalkyl group, and the like. A fluoroalkyl group is preferable, and a perfluoroalkyl group is particularly preferable. More specifically, for example, fluoromethyl group, perfluoromethyl group, fluoroethyl group, perfluoroethyl group, fluoro-n-propyl group, perfluoro-n-propyl group, fluoro-n-butyl group, perfluoro- n-butyl group, fluoro-n-pentyl group, perfluoro-n-pentyl group, fluoro-n-hexyl group, perfluoro-n-hexyl group, chloromethyl group, perchloromethyl group, chloroethyl group, perchloroethyl Group, chloro-n-propyl group, perchloro-n-propyl group, chloro-n-butyl group, perchloro-n-butyl group, chloro-n-pentyl group, perchloro-n-pentyl group, chloro-n-hexyl group Perchloro-n-hexyl group, bromomethyl group, perbromomethyl group, bromoethyl group, perbromoethyl group, bromo-n-propyl group, perbromo-n-pro Group, bromo-n-butyl group, perbromo-n-butyl group, bromo-n-pentyl group, perbromo-n-pentyl group, bromo-n-hexyl group, perbromo-n-hexyl group, etc. Perfluoromethyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro-n-pentyl group, and perfluoro-n-hexyl group are preferable. A fluoroethyl group and a perfluoro-n-propyl group are more preferable.

The alkoxy group as the substituent of the aryl group having 6 to 10 carbon atoms in R ₁ to R ₃ usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, specifically, for example, a methoxy group, Examples include ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, methoxy group, ethoxy group N-propoxy group, isopropoxy group, tert-butoxy group and the like are preferable.

As the aryl group having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent in R ₁ to R ₃ , an aryl group having a halogeno group as a substituent, An aryl group having an alkyl group as a substituent, an aryl group having an alkoxy group as a substituent, an unsubstituted aryl group, and the like are preferable. In addition, the number of substituents of the aryl group having 6 to 10 carbon atoms having a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent in R ₁ to R ₃ is usually 1 to 7, preferably 1. ~ 5, more preferably 1-2.

Specific examples of the aryl group having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent in R ₁ to R ₃ include a phenyl group and a naphthyl group. Fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, perfluorophenyl group, perchlorophenyl group, perbromophenyl group, periododophenyl group; methylphenyl group, ethylphenyl group, n-propylphenyl group, isopropyl Phenyl group, n-butylphenyl group, isobutylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, isopentylphenyl group, sec-pentylphenyl group, tert-pentylphenyl group, neopentyl Phenyl group, n-hexylpheny Group, isohexylphenyl group, sec-hexylphenyl group, tert-hexylphenyl group, 3-methylpentylphenyl group, 2-methylpentylphenyl group, 1,2-dimethylbutylphenyl group, cyclopropylphenyl group, cyclopentylphenyl Group, cyclohexylphenyl group; fluoromethylphenyl group, perfluoromethylphenyl group, fluoroethylphenyl group, perfluoroethylphenyl group, fluoro-n-propylphenyl group, perfluoro-n-propylphenyl group, fluoroisopropylphenyl group, Perfluoroisopropylphenyl group, fluoro-n-butylphenyl group, perfluoro-n-butylphenyl group, fluoroisobutylphenyl group, perfluoroisobutylphenyl group, fluoro-sec-butylphenyl group, perfluoro-sec-butyl group Tilphenyl group, fluoro-tert-butylphenyl group, perfluoro-tert-butylphenyl group, fluoro-n-pentylphenyl group, perfluoro-n-pentylphenyl group, fluoroisopentylphenyl group, perfluoroisopentylphenyl group, Fluoro-sec-pentylphenyl group, perfluoro-sec-pentylphenyl group, fluoro-tert-pentylphenyl group, perfluoro-tert-butylphenyl group, fluoroneopentylphenyl group, perfluoroneopentylphenyl group, fluoro-n -Hexylphenyl group, perfluoro-n-hexylphenyl group, fluoroisohexylphenyl group, perfluoroisohexylphenyl group, fluoro-sec-hexylphenyl group, perfluoro-sec-hexylphenyl group, fluoro-tert-hexylphenyl Group, perfluoro-tert-he Xylphenyl group, fluoro-3-methylpentylphenyl group, perfluoro-3-methylpentylphenyl group, fluoro-2-methylpentylphenyl group, perfluoro-2-methylpentylphenyl group, fluoro-1,2-dimethylbutyl Phenyl group, perfluoro-1,2-dimethylbutylphenyl group, fluorocyclopropylphenyl group, perfluorocyclopropylphenyl group, fluorocyclobutylphenyl group, perfluorocyclobutylphenyl group, fluorocyclopentylphenyl group, perfluorocyclopentylphenyl Group, fluorocyclohexylphenyl group, perfluorocyclohexylphenyl group, chloromethylphenyl group, perchloromethylphenyl group, chloroethylphenyl group, perchloroethylphenyl group, chloro-n-propylphenyl group, -Chloro-n-propylphenyl group, chloroisopropylphenyl group, perchloroisopropylphenyl group, chloro-n-butylphenyl group, perchloro-n-butylphenyl group, chloroisobutylphenyl group, perchloroisobutylphenyl group, chloro-sec- Butylphenyl group, perchloro-sec-butylphenyl group, chloro-tert-butylphenyl group, perchloro-tert-butylphenyl group, chloro-n-pentylphenyl group, perchloro-n-pentylphenyl group, chloroisopentylphenyl group, Perchloroisopentylphenyl, chloro-sec-pentylphenyl, perchloro-sec-pentylphenyl, chloro-tert-pentylphenyl, perchloro-tert-butylphenyl, chloroneopentylphenyl, perchloroneopentylphenyl Group, chloro-n-hexyl Phenyl group, perchloro-n-hexylphenyl group, chloroisohexylphenyl group, perchloroisohexylphenyl group, chloro-sec-hexylphenyl group, perchloro-sec-hexylphenyl group, chloro-tert-hexylphenyl group, perchloro- tert-hexylphenyl group, chloro-3-methylpentylphenyl group, perchloro-3-methylpentylphenyl group, chloro-2-methylpentylphenyl group, perchloro-2-methylpentylphenyl group, chloro-1,2-dimethylbutyl Phenyl group, perchloro-1,2-dimethylbutylphenyl group, chlorocyclopropylphenyl group, perchlorocyclopropylphenyl group, chlorocyclobutylphenyl group, perchlorocyclobutylphenyl group, chlorocyclopentylphenyl group, perchlorocyclopentylphenyl group , Chlorocyclo Hexylphenyl group, perchlorocyclohexylphenyl group, bromomethylphenyl group, perbromomethylphenyl group, bromoethylphenyl group, perbromoethylphenyl group, bromo-n-propylphenyl group, perbromo-n-propylphenyl group, bromoisopropyl Phenyl group, perbromoisopropylphenyl group, bromo-n-butylphenyl group, perbromo-n-butylphenyl group, bromoisobutylphenyl group, perbromoisobutylphenyl group, bromo-sec-butylphenyl group, perbromo-sec-butylphenyl Group, bromo-tert-butylphenyl group, perbromo-tert-butylphenyl group, bromo-n-pentylphenyl group, perbromo-n-pentylphenyl group, bromoisopentylphenyl group, perbromoisopentylphenyl group, bromo-sec -Pliers Phenyl group, perbromo-sec-pentylphenyl group, bromo-tert-pentylphenyl group, perbromo-tert-butylphenyl group, bromoneopentylphenyl group, perbromoneopentylphenyl group, bromo-n-hexylphenyl group, perbromo- n-hexylphenyl group, bromoisohexylphenyl group, perbromoisohexylphenyl group, bromo-sec-hexylphenyl group, perbromo-sec-hexylphenyl group, bromo-tert-hexylphenyl group, perbromo-tert-hexylphenyl group Bromo-3-methylpentylphenyl group, perbromo-3-methylpentylphenyl group, bromo-2-methylpentylphenyl group, perbromo-2-methylpentylphenyl group, bromo-1,2-dimethylbutylphenyl group, perbromo- 1,2-dimethylbutylphenyl group, bromocyclopropyl group Enyl group, perbromocyclopropylphenyl group, bromocyclobutylphenyl group, perbromocyclobutylphenyl group, bromocyclopentylphenyl group, perbromocyclopentylphenyl group, bromocyclohexylphenyl group, perbromocyclohexylphenyl group; methoxyphenyl group, ethoxy Phenyl group, n-propoxyphenyl group, isopropoxyphenyl group, n-butoxyphenyl group, isobutoxyphenyl group, sec-butoxyphenyl group, tert-butoxyphenyl group, n-pentyloxyphenyl group, isopentyloxyphenyl group, sec-pentyloxyphenyl group, tert-pentyloxyphenyl group, neopentyloxyphenyl group, n-hexyloxyphenyl group, isohexyloxyphenyl group, sec-hexyloxyphenyl group Nyl group, tert-hexyloxyphenyl group, 3-methylpentyloxyphenyl group, 2-methylpentyloxyphenyl group, 1,2-dimethylbutoxyphenyl group, cyclopropyloxyphenyl group, cyclobutyloxyphenyl group, cyclopentyloxyphenyl Group, cyclohexyloxyphenyl group and the like.

Among the above specific examples, phenyl group, methylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, isobutylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n -Pentylphenyl group, isopentylphenyl group, sec-pentylphenyl group, tert-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, isohexylphenyl group, sec-hexylphenyl group, tert-hexylphenyl group, 3-methylpentylphenyl group, 2-methylpentylphenyl group, 1,2-dimethylbutylphenyl group, cyclopropylphenyl group, cyclopentylphenyl group, cyclohexylphenyl group; fluoromethylphenyl group, perfluoromethylphenyl group, fluoro Tylphenyl group, perfluoroethylphenyl group, fluoro-n-propylphenyl group, perfluoro-n-propylphenyl group, fluoro-n-butylphenyl group, perfluoro-n-butylphenyl group, fluoro-n-pentylphenyl group Perfluoro-n-pentylphenyl group, fluoro-n-hexylphenyl group, perfluoro-n-hexylphenyl group, chloromethylphenyl group, perchloromethylphenyl group, chloroethylphenyl group, perchloroethylphenyl group, chloro -n-propylphenyl group, perchloro-n-propylphenyl group, chloro-n-butylphenyl group, perchloro-n-butylphenyl group, chloro-n-pentylphenyl group, perchloro-n-pentylphenyl group, chloro-n -Hexylphenyl group, perchloro-n-hexylphenyl group, bromo Tylphenyl group, perbromomethylphenyl group, bromoethylphenyl group, perbromoethylphenyl group, bromo-n-propylphenyl group, perbromo-n-propylphenyl group, bromo-n-butylphenyl group, perbromo-n-butylphenyl Group, bromo-n-pentylphenyl group, perbromo-n-pentylphenyl group, bromo-n-hexylphenyl group, perbromo-n-hexylphenyl group; methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, isopropoxy A phenyl group, an n-butoxyphenyl group, an isobutoxyphenyl group, a sec-butoxyphenyl group, a tert-butoxyphenyl group, an n-pentyloxyphenyl group, an n-hexyloxyphenyl group and the like are preferable, and a phenyl group, a methylphenyl group, Ethylphenyl group, n-propiyl Phenyl group, isopropylphenyl group; fluoromethylphenyl group, chloromethylphenyl group, bromomethylphenyl group, iodomethylphenyl group; methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, isopropoxyphenyl group, tert-butoxy A phenyl group or the like is more preferable.

The alkenyl group having 1 to 6 carbon atoms in R ₂ and R ₃ of the compound represented by the general formula (I) may be linear, branched or cyclic, and preferably has 1 to 3 carbon atoms. Specifically, for example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 3-butenyl group, 2-butenyl group, 1-butenyl group, 1,3-butadienyl group, 4-pentenyl group, 3- Examples include pentenyl group, 2-pentenyl group, 1-pentenyl group, 1-methyl-1-butenyl group, 5-hexenyl group, 4-hexenyl group, 3-hexenyl group, 2-hexenyl group, 1-hexenyl group, etc. Of these, a vinyl group, an allyl group, a 1-propenyl group and an isopropenyl group are preferable, and an allyl group is more preferable.

The alkyl group having 1 to 6 carbon atoms in R ₂ and R ₃ of the compound represented by the general formula (I) preferably has 1 to 4 carbon atoms, and may be linear, branched or cyclic. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group Tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, 3-methylpentyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, cyclopentyl group, Examples thereof include a cyclohexyl group, and a methyl group, an ethyl group, an n-propyl group, and an n-butyl group are preferable.

Examples of the halogeno group as a substituent of the alkyl group having 1 to 6 carbon atoms in R ₂ and R ₃ include a fluoro group, a chloro group, a bromo group, and an iodo group, and a fluoro group is preferred.

The alkoxy group as a substituent of the alkyl group having 1 to 6 carbon atoms in R ₁ to R ₃ usually has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, specifically, for example, a methoxy group, Examples include ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, methoxy group, ethoxy group N-propoxy group, isopropoxy group and the like are preferable.

Specific examples of the alkyl group having 1 to 6 carbon atoms which may have a halogeno group or an alkoxy group as a substituent in R ₁ to R ₃ include, for example, methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec -Hexyl group, tert-hexyl group, 3-methylpentyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, cyclopentyl group, cyclohexyl group; perfluoromethyl group, perfluoroethyl group, perfluoro-n- Propyl group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group, Perfluoro-tert-butyl group, perfluoro-n-pentyl group, perfluoroisopentyl group, perfluoro-sec-pentyl group, perfluoro-tert-pentyl group, perfluoroneopentyl group, perfluoro-n-hexyl Group, perfluoroisohexyl group, perfluoro-sec-hexyl group, perfluoro-tert-hexyl group, perfluoro-3-methylpentyl group, perfluoro-2-methylpentyl group, perfluoro-1,2-dimethyl group Butyl group, perfluorocyclopentyl group, perfluorocyclohexyl group, fluoromethyl group, fluoroethyl group, fluoro-n-propyl group, fluoroisopropyl group, fluoro-n-butyl group, fluoroisobutyl group, fluoro-sec-butyl group, Fluoro-tert-butyl group, fluoro-n-pentyl group, fluoroisopentyl group, Fluoro-sec-pentyl group, fluoro-tert-pentyl group, fluoroneopentyl group, fluoro-n-hexyl group, fluoroisohexyl group, fluoro-sec-hexyl group, fluoro-tert-hexyl group, fluoro-3-methyl Pentyl group, fluoro-2-methylpentyl group, fluoro-1,2-dimethylbutyl group, fluorocyclopentyl group, fluorocyclohexyl group; perchloromethyl group, perchloroethyl group, perchloro-n-propyl group, perchloroisopropyl group Perchloro-n-butyl, perchloro-sec-butyl, perchloro-tert-butyl, perchloro-n-pentyl, perchloroisopentyl, perchloro-sec-pentyl, perchloro-tert-pentyl, perchloro Chloroneopentyl group, perchloro-n-hexyl group, perchloroisohexyl group Perchloro-sec-hexyl group, perchloro-tert-hexyl group, perchloro-3-methylpentyl group, perchloro-2-methylpentyl group, perchloro-1,2-dimethylbutyl group, perchlorocyclopentyl group, perchlorocyclohexyl group , Chloromethyl group, chloroethyl group, chloro-n-propyl group, chloroisopropyl group, chloro-n-butyl group, chloroisobutyl group, chloro-sec-butyl group, chloro-tert-butyl group, chloro-n-pentyl group , Chloroisopentyl group, chloro-sec-pentyl group, chloro-tert-pentyl group, chloroneopentyl group, chloro-n-hexyl group, chloroisohexyl group, chloro-sec-hexyl group, chloro-tert-hexyl group Chloro-3-methylpentyl group, chloro-2-methylpentyl group, chloro-1,2-dimethylbutyl group, chlorocyclopentyl group, Chlohexyl group; perbromomethyl group, perbromoethyl group, perbromo-n-propyl group, perbromoisopropyl group, perbromo-n-butyl group, perbromo-sec-butyl group, perbromo-tert-butyl group, perbromo-n- Pentyl group, perbromoisopentyl group, perbromo-sec-pentyl group, perbromo-tert-pentyl group, perbromoneopentyl group, perbromo-n-hexyl group, perbromoisohexyl group, perbromo-sec-hexyl group, perbromo -tert-hexyl group, perbromo-3-methylpentyl group, perbromo-2-methylpentyl group, perbromo-1,2-dimethylbutyl group, perbromocyclopentyl group, perbromocyclohexyl group, bromomethyl group, bromoethyl group, bromo- n-propyl, bromoisopropyl, bromo-n-butyl, butyl Lomoisobutyl, bromo-sec-butyl, bromo-tert-butyl, bromo-n-pentyl, bromoisopentyl, bromo-sec-pentyl, bromo-tert-pentyl, bromoneopentyl, bromo -n-hexyl group, bromoisohexyl group, bromo-sec-hexyl group, bromo-tert-hexyl group, bromo-3-methylpentyl group, bromo-2-methylpentyl group, bromo-1,2-dimethylbutyl group Bromocyclopentyl group, bromocyclohexyl group; periodomethyl group, periodoethyl group, periodo-n-propyl group, periodioisopropyl group, periodo-n-butyl group, periodo-sec-butyl group, periodo-tert-butyl Group, Periodo-n-pentyl group, Periodoisopentyl group, Periodo-sec-pentyl group, Periodo-tert-pentyl group, Periodo neopen Til, period-n-hexyl, period-isohexyl, period-sec-hexyl, period-tert-hexyl, periodio-3-methylpentyl, period-2-methylpentyl, period-1, 2-dimethylbutyl group, periodocyclopentyl group, periodocyclohexyl group, iodomethyl group, iodoethyl group, iodo-n-propyl group, iodoisopropyl group, iodo-n-butyl group, iodoisobutyl group, iodo-sec-butyl group , Iodo-tert-butyl, iodo-n-pentyl, iodoisopentyl, iodo-sec-pentyl, iodo-tert-pentyl, iodoneopentyl, iodo-n-hexyl, iodoisohexyl Iodo-sec-hexyl group, iodo-tert-hexyl group, iodo-3-methylpentyl group, iodo-2-methylpentyl group, 1,2-dimethylbutyl group, iodocyclopentyl group, iodocyclohexyl group; methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec- Butoxymethyl group, tert-butoxymethyl group, n-pentyloxymethyl group, neopentyloxymethyl group, n-hexyloxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n -Butoxyethyl group, isobutoxyethyl group, sec-butoxyethyl group, tert-butoxyethyl group, n-pentyloxyethyl group, neopentyloxyethyl group, n-hexyloxyethyl group, methoxy-n-propyl group, ethoxy -n-propyl group, n-propoxy-n-propyl group Isopropoxy-n-propyl group, n-butoxy-n-propyl group, isobutoxy-n-propyl group, sec-butoxy-n-propyl group, tert-butoxy-n-propyl group, n-pentyloxy-n-propyl Group, neopentyloxy-n-propyl group, n-hexyloxy-n-propyl group, methoxy-n-butyl group, ethoxy-n-butyl group, n-propoxy-n-butyl group, isopropoxy-n-butyl Group, n-butoxy-n-butyl group, isobutoxy-n-butyl group, sec-butoxy-n-butyl group, tert-butoxy-n-butyl group, n-pentyloxy-n-butyl group, neopentyloxy- Examples thereof include n-butyl group and n-hexyloxy-n-butyl group.

Among them, perfluoromethyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, methoxy A methyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group and the like are preferable.

R ₂ and R ₃ in the compound represented by the general formula (I) are a magnesium chlorideoxy group (—OMgCl); an alkenyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms; or a halogeno group or an alkyl group An aryl group having 6 to 10 carbon atoms which may have a halogenoalkyl group or an alkoxy group as a substituent, magnesium chlorideoxy group (—OMgCl); alkenyl group having 1 to 6 carbon atoms; An alkyl group having 6 to 6; or an aryl group having 6 to 10 carbon atoms which may have an alkyl group as a substituent is more preferable. Specific examples of these include magnesium chlorideoxy group (-OMgCl), vinyl group, allyl group, 1-propenyl group, isopropenyl group, methyl group, ethyl group, n-propyl group, n-butyl group, phenyl group, Methylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group; fluoromethylphenyl group, chloromethylphenyl group, bromomethylphenyl group, iodomethylphenyl group; methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl Group, isopropoxyphenyl group, tert-butoxyphenyl group, etc., magnesium chlorideoxy group (-OMgCl), vinyl group, allyl group, 1-propenyl group, isopropenyl group, methyl group, ethyl group, n-propyl Group, n-butyl group, phenyl group, methylphenyl group, ethylpheny More preferred are an alkyl group, an n-propylphenyl group, an isopropylphenyl group, and the like.

Preferable specific examples of the compound represented by the general formula (I) include compounds represented by the following general formula (II), (I-II) or (I-III).

(Wherein R ₄ , R ₅ and R ₆ each independently represents a halogeno group, an alkyl group, a halogenoalkyl group or an alkoxy group, and n4, n5 and n6 each independently represents 0 to 5) (X and Y are the same as above.)

(Wherein R ₇ represents a magnesium chlorideoxy group (—OMgCl); an alkenyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; R ₄ , R ₆ , n4, n6 and X, Y Is the same as above.)

(In the formula, two R _{8 s} independently represent a magnesium chlorideoxy group (—OMgCl); an alkenyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; R ₄ , n4, X And Y are the same as above.)

In the compound represented by (II), (I-II) or (I-III), Y is preferably a silicon atom. X is preferably a chlorine atom.

The halogeno group, alkyl group, halogenoalkyl group, or alkoxy group in R ₄ , R _5, and R ₆ is preferably a halogeno group, an alkyl group, or an alkoxy group. Specific examples thereof include the same as those described as the substituent of the aryl group having 6 to 10 carbon atoms in R ₁ to R ₃ , and preferable examples thereof are also the same.

The above n4, n5, and n6 are preferably 0-2.

Specific examples of the alkenyl group having 1 to 6 carbon atoms and the alkyl group having 1 to 6 carbon atoms in the above R ₇ and R ₈ include the alkenyl group having 1 to 6 carbon atoms and the alkyl group having 1 to 6 carbon atoms in R ₂ and R ₃ , respectively. The same thing as the alkyl group of 6 is mentioned, A preferable thing is also the same.

R ₇ is preferably a magnesium chlorideoxy group (—OMgCl) or an alkenyl group having 1 to 6 carbon atoms. R ₈ is preferably an alkyl group having 1 to 6 carbon atoms.

[Lewis acid]
Lewis acids according to the present invention include beryllium (Be), boron (B), aluminum (Al), silicon (Si), tin (Sn), titanium (Ti), chromium (Cr), iron (Fe), cobalt ( Co) is included as an element. Specifically, beryllium compounds such as beryllium fluoride (II), beryllium chloride (II), and beryllium bromide (II); boron chloride (III), boron fluoride (III), boron bromide (III), tri Boron compounds such as phenoxyborane, phenyldichloroborane, triphenylborane; aluminum chloride (III), aluminum bromide (III), aluminum iodide (III), dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride Aluminum compounds such as trimethylaluminum and triethylaluminum; silyl compounds such as trimethylsilyl triflate, trimethylsilyliodo, tert-butyldimethylsilyl triflate and triisopropylsilyl triflate; tin chloride (IV , Tin compounds such as tin (IV) bromide, tin (II) chloride, tin (II) triflate; titanium chloride (IV), titanium fluoride (IV), titanium bromide (IV), titanium iodide (IV) Titanium compounds such as chromium fluoride (II), chromium fluoride (III), chromium chloride (II), chromium chloride (III), chromium bromide (II), chromium bromide (III), chromium iodide (II) ), Chromium compounds such as chromium (III) iodide; iron compounds such as iron fluoride (II), iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (II) iodide Or cobalt compounds such as cobalt fluoride (II), cobalt chloride (II), cobalt bromide (II) and cobalt iodide (II).

Among these, a boron compound or an aluminum compound is preferable, and an aluminum compound is more preferable. Specifically, aluminum chloride (III), methylaluminum dichloride, dimethylaluminum chloride, boron chloride (III) and the like are preferable, and aluminum chloride (III) is particularly preferable.

[solvent]
As the solvent according to the present invention, those capable of dissolving the compound represented by the general formula (I) according to the present invention are preferable. Examples of such solvents include ether solvents, halogenated hydrocarbon solvents, carbonate solvents, nitrile solvents, sulfone solvents, and the like.

Examples of the ether solvent include diethyl ether, diglyme, triglyme, tetraglyme, tetrahydrofuran, 2-methyltetrahydrofuran, diisopropyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, cyclopentyl methyl ether, and t-butyl. Examples of the halogenated hydrocarbon solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and the like. Examples of the carbonate solvent include dimethyl carbonate. , Diethyl carbonate, ethyl methyl carbonate, propylene carbonate and the like; examples of nitrile solvents include acetonitrile, propionitrile, butyronitrile, succino Examples of the sulfone solvent include sulfolane, dimethyl sulfone, ethyl methyl sulfone, methyl-n-propyl sulfone, methyl isopropyl sulfone, n-butyl-methyl sulfone, and isobutyl methyl. Sulfone, sec-butylmethylsulfone, tert-butylmethylsulfone, diethylsulfone, ethyl-n-propylsulfone, ethylisopropylsulfone, n-butylethylsulfone, isobutylethylsulfone, sec-butylethylsulfone, tert-butylethylsulfone, Di-n-propylsulfone, diisopropylsulfone, n-butyl-n-propylsulfone, di-n-butylsulfone and the like can be mentioned.
Among the above specific examples, ether solvents, sulfone solvents and the like are preferable, specifically, 1,2-dimethoxyethane, diglyme, triglyme, tetraglyme, tetrahydrofuran, sulfolane are particularly preferable, diglyme, triglyme, tetraglyme, Tetrahydrofuran is particularly preferred.
The solvent according to the present invention may be a mixture of two or more of the above solvents.

[Electrolyte]
The electrolytic solution of the present invention is obtained by mixing the compound represented by the general formula (I) according to the present invention and the Lewis acid according to the present invention in the solvent according to the present invention.

The concentration of the compound represented by the general formula (I) in the electrolytic solution is usually 0.1 to 5 mol / mL, preferably 0.1 to 3 mol / mL, more preferably 0.2 to 2 mol / mL.

The amount of Lewis acid used in the electrolytic solution of the present invention is usually 0.1 to 5 mol times, preferably 0.1 to 3 mol times that of the compound represented by the general formula (I) according to the present invention.

The electrolytic solution of the present invention contains additives such as a film forming agent, an overcharge inhibitor, an oxygen scavenger, a dehydrating agent, a flame retardant and the like and a coordinating additive such as crown ether, which are usually used in this field. Also good.

Such an electrolytic solution of the present invention can be used for a magnesium battery, and in the case of a magnesium secondary battery, it exhibits a high oxidative decomposition potential and can be used stably and repeatedly.

The electrolytic solution of the present invention is produced by dissolving (mixing) the compound represented by the general formula (I) according to the present invention and the Lewis acid according to the present invention in the solvent according to the present invention. More specifically, 0.1 to 5 mol of the Lewis acid according to the present invention is used with respect to 1 mol of the compound represented by the general formula (I) according to the present invention, and the concentration is adjusted to the above concentration. It is manufactured by adding to such a solvent and mixing. In addition, it may be heated or cooled in the range of −78 to 300 ° C. as necessary during mixing, preferably 0 to 70 ° C.

[Electrochemical devices]
The electrochemical device of the present invention has a positive electrode, a negative electrode, and an electrolytic solution of the present invention. Specifically, a primary battery, a secondary battery, an electric double layer capacitor and the like can be mentioned, and among them, a secondary battery is preferable.

The positive electrode in the electrochemical device of the present invention is not particularly limited as long as it can contain magnesium or magnesium ions inside, on the surface and in the vicinity thereof. Specifically, for example, an oxide containing cobalt, manganese, vanadium, aluminum, iron, silicon, phosphorus, nickel, molybdenum, titanium, or the like, or an electrode containing sulfide as an active material can be given.

Further, the positive electrode may contain an active material capable of adsorbing and storing magnesium such as sulfur or magnesium ions, an organic chemical substance having high oxidizing power, and a material forming an electric double layer such as porous carbon or activated carbon. Well, magnesium may be included in an oxidized form.

The negative electrode in the electrochemical device of the present invention is not particularly limited as long as it can contain magnesium or magnesium ions inside, on the surface, or in the vicinity thereof. Specific examples include metal magnesium capable of dissolving and precipitating magnesium, a magnesium alloy, a metal that can be alloyed with magnesium, a carbon material capable of intercalating magnesium or magnesium ions, and the like.

Moreover, the electrochemical device of the present invention may further have a separator in addition to the positive electrode, the negative electrode, and the electrolytic solution of the present invention. The separator is not particularly limited as long as it electrically insulates the positive electrode and the negative electrode and can permeate magnesium ions, and examples thereof include a microporous polymer film such as a porous polyolefin film. Specific examples of the porous polyolefin film include, for example, a porous polyethylene film alone or a multilayer film obtained by superposing a porous polyethylene film and a porous polypropylene film.

[Compound represented by the general formula (I ′)]
X of the compound represented by the general formula (I ′) represents a chlorine atom or a bromine atom, and a chlorine atom is preferable.

R ′ _{1 of the} compound represented by the general formula (I ′) represents a halogeno group, an alkyl group, a halogenoalkyl group, or an aryl group having 6 to 10 carbon atoms which may have an alkoxy group as a substituent, Specific examples and preferable examples of the aryl group having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent include R of the compound represented by the general formula (I). _The same thing as ₁ is mentioned.

R ′ ₂ and R ′ _{3 in the} compound represented by the general formula (I ′) are each independently selected from: a magnesium chlorideoxy group (—OMgCl); an alkenyl group having 1 to 6 carbon atoms; a halogeno group or an alkoxy group. An alkyl group having 1 to 6 carbon atoms which may have a substituent; or an aryl having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, a halogenoalkyl group or an alkoxy group as a substituent. Represents a group. An alkenyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms which may have a halogeno group or an alkoxy group as a substituent; and a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group is substituted. Specific examples and preferred examples of the aryl group having 6 to 10 carbon atoms which may be present as a group include the same as R ₂ and R _{3 of the} compound represented by the general formula (I).
Preferable specific examples of R ′ ₂ and R ′ ₃ include the same as R ₂ and R _{3 of the} compound represented by the general formula (I).

Specific examples of the compound represented by the general formula (I ′) include, for example, a magnesium bromide compound, specifically, triphenylsiloxymagnesium bromide; tris (2-methylphenyl) siloxymagnesium bromide, tris (3- Methylphenyl) siloxymagnesium bromide, tris (4-methylphenyl) siloxymagnesium bromide, tris (2,2-dimethylphenyl) siloxymagnesium bromide, tris (3,3-dimethylphenyl) siloxymagnesium bromide, tris (2,3- Dimethylphenyl) siloxymagnesium bromide, tris (2,4-dimethylphenyl) siloxymagnesium bromide, tris (3,4-dimethylphenyl) siloxymagnesium bromide, tris (2,4,6-trimethylphenyl) siloxymagnesium bromide , Tris (2,3,4,5-tetramethylphenyl) siloxymagnesium bromide, Tris (2,3,4,6-tetramethylphenyl) siloxymagnesium bromide, Tris (2,3,5,6-tetramethylphenyl) ) Siloxymagnesium bromide, Tris (2,3,4,5,6-pentamethylphenyl) siloxymagnesium bromide; Tris (2-fluorophenyl) siloxymagnesium bromide, Tris (3-fluorophenyl) siloxymagnesium bromide, Tris (4 -Fluorophenyl) siloxymagnesium bromide, tris (2,2-difluorophenyl) siloxymagnesium bromide, tris (3,3-difluorophenyl) siloxymagnesium bromide, tris (2,3-difluorophenyl) siloxymagnesium bromide, tris (2 , 4-Difluorophenyl) siloxymagnesi Mubromide, Tris (3,4-difluorophenyl) siloxymagnesium bromide, Tris (2,4,6-trifluorophenyl) siloxymagnesium bromide, Tris (2,3,4,5-tetrafluorophenyl) siloxymagnesium bromide, Tris (2,3,4,6-tetrafluorophenyl) siloxymagnesium bromide, tris (2,3,5,6-tetrafluorophenyl) siloxymagnesium bromide, tris (2,3,4,5,6-pentafluorophenyl) ) Siloxymagnesium bromide; Tris (2-methoxyphenyl) siloxymagnesium bromide, Tris (3-methoxyphenyl) siloxymagnesium bromide, Tris (4-methoxyphenyl) siloxymagnesium bromide, Tris (2,2-dimethoxyphenyl) siloxymagnesium bromide , Tris (3,3-dimethoxyphene L) Siloxymagnesium bromide, Tris (2,3-dimethoxyphenyl) siloxymagnesium bromide, Tris (2,4-dimethoxyphenyl) siloxymagnesium bromide, Tris (3,4-dimethoxyphenyl) siloxymagnesium bromide, Tris (2,4 , 6-Trimethoxyphenyl) siloxymagnesium bromide, Tris (2,3,4,5-tetramethoxyphenyl) siloxymagnesium bromide, Tris (2,3,4,6-tetramethoxyphenyl) siloxymagnesium bromide, Tris (2 , 3,5,6-tetramethoxyphenyl) siloxymagnesium bromide, tris (2,3,4,5,6-pentamethoxyphenyl) siloxymagnesium bromide; dimethylphenylsiloxymagnesium bromide, methyldiphenylsiloxymagnesium bromide, diethylphenylsiloxy Magnesium bromide, ethyldiphenylsiloxymagnesium bromide, di (tert-butyl) phenylsiloxymagnesium bromide, tert-butyldiphenylsiloxymagnesium bromide; dimethyl (methylphenyl) siloxymagnesium bromide, methyldi (methylphenyl) siloxymagnesium bromide, dimethyl (dimethylphenyl) ) Siloxymagnesium bromide, methyldi (dimethylphenyl) siloxymagnesium bromide, dimethyl (trimethylphenyl) siloxymagnesium bromide, methyldi (trimethylphenyl) siloxymagnesium bromide, dimethyl (tetramethylphenyl) siloxymagnesium bromide, methyldi (tetramethylphenyl) siloxymagnesium Bromide, dimethyl (pentamethylphen Nyl) siloxymagnesium bromide, methyldi (pentamethylphenyl) siloxymagnesium bromide; dimethyl (fluorophenyl) siloxymagnesium bromide, methyldi (fluorophenyl) siloxymagnesium bromide, dimethyl (difluorophenyl) siloxymagnesium bromide, methyldi (difluorophenyl) siloxymagnesium Bromide, dimethyl (trifluorophenyl) siloxymagnesium bromide, methyldi (trifluorophenyl) siloxymagnesium bromide, dimethyl (tetrafluorophenyl) siloxymagnesium bromide, methyldi (tetrafluorophenyl) siloxymagnesium bromide, dimethyl (pentafluorophenyl) siloxymagnesium Bromide, methyldi (penta Fluorophenyl) siloxymagnesium bromide; dimethyl (methoxyphenyl) siloxymagnesium bromide, methyldi (methoxyphenyl) siloxymagnesium bromide, dimethyl (dimethoxyphenyl) siloxymagnesium bromide, methyldi (dimethoxyphenyl) siloxymagnesium bromide, dimethyl (trimethoxyphenyl) siloxy Magnesium bromide, methyldi (trimethoxyphenyl) siloxymagnesium bromide, dimethyl (tetramethoxyphenyl) siloxymagnesium bromide, methyldi (tetramethoxyphenyl) siloxymagnesium bromide, dimethyl (pentamethoxyphenyl) siloxymagnesium bromide, methyldi (pentamethoxyphenyl) siloxy Magnesium bromide; Di Til (trifluoromethylphenyl) siloxymagnesium bromide, methyldi (trifluoromethylphenyl) siloxymagnesium bromide, dimethyl (di (trifluoromethyl) phenyl) siloxymagnesium bromide, methyldi (di (trifluoromethyl) phenyl) siloxymagnesium bromide, Dimethyl (tri (trifluoromethyl) phenyl) siloxymagnesium bromide, methyldi (tri (trifluoromethyl) phenyl) siloxymagnesium bromide, dimethyl (tetra (trifluoromethyl) phenyl) siloxymagnesium chloride, methyldi (tetra (trifluoromethyl) Phenyl) siloxymagnesium bromide, dimethyl (penta (trifluoromethyl) phenyl) siloxymagnesium bromide, Tildi (penta (trifluoromethyl) phenyl) siloxymagnesium bromide, di (tert-butyl) (trifluoromethylphenyl) siloxymagnesium bromide, methyldi (trifluoromethylphenyl) siloxymagnesium bromide, dimethyl (di (trifluoromethyl) phenyl ) Siloxymagnesium bromide, methyldi (di (trifluoromethyl) phenyl) siloxymagnesium bromide, dimethyl (trifluoro (trifluoromethyl) phenyl) siloxymagnesium bromide, methyldi (tri (trifluoromethyl) phenyl) siloxymagnesium bromide, dimethyl (tetra (Trifluoromethyl) phenyl) siloxymagnesium bromide, methyldi (tetra (trifluoromethyl) phenyl) siloxymagnesium Lomid, dimethyl (penta (trifluoromethyl) phenyl) siloxymagnesium bromide, methyldi (penta (trifluoromethyl) phenyl) siloxymagnesium bromide; diphenylsilanedioxybis (magnesium bromide), di (methylphenyl) silanedioxybis ( Magnesium bromide), di (dimethylphenyl) silanedioxybis (magnesium bromide), di (trimethylphenyl) silanedioxybis (magnesium bromide), di (tetramethylphenyl) silanedioxybis (magnesium bromide), di (penta Methylphenyl) silanedioxybis (magnesium bromide); di (fluorophenyl) silanedioxybis (magnesium bromide), di (difluorophenyl) silanedioxybis Magnesium bromide), di (trifluorophenyl) silane dioxybis (magnesium bromide), di (tetrafluorophenyl) silane dioxybis (magnesium bromide), di (pentafluorophenyl) silane dioxybis (magnesium bromide); (Methoxyphenyl) silanedioxybis (magnesium bromide), di (dimethoxyphenyl) silanedioxybis (magnesium bromide), di (trimethoxyphenyl) silanedioxybis (magnesium bromide), di (tetramethoxyphenyl) silanedi Oxybis (magnesium bromide), di (pentamethoxyphenyl) silanedioxybis (magnesium bromide); di (trifluoromethylphenyl) silanedioxybis (magnesium bromide), di ( Di (trifluoromethyl) phenyl) silanedioxybis (magnesium bromide), di (tri (trifluoromethyl) phenyl) silanedioxybis (magnesium bromide), di (tetra (trifluoromethyl) phenyl) silanedioxybis (Magnesium bromide), di (penta (trifluoromethyl) phenyl) silanedioxybis (magnesium bromide), and the like.

Specific examples of the compound represented by the general formula (I ′) include, for example, a magnesium chloride compound, specifically, triphenylsiloxymagnesium chloride; tris (2-methylphenyl) siloxymagnesium chloride, tris ( 3-methylphenyl) siloxymagnesium chloride, tris (4-methylphenyl) siloxymagnesium chloride, tris (2,2-dimethylphenyl) siloxymagnesium chloride, tris (3,3-dimethylphenyl) siloxymagnesium chloride, tris (2, 3-dimethylphenyl) siloxymagnesium chloride, tris (2,4-dimethylphenyl) siloxymagnesium chloride, tris (3,4-dimethylphenyl) siloxymagnesium chloride, tris (2,4,6-trimethylphenyl) siloxymagnesium Loride, Tris (2,3,4,5-tetramethylphenyl) siloxymagnesium chloride, Tris (2,3,4,6-tetramethylphenyl) siloxymagnesium chloride, Tris (2,3,5,6-tetramethyl Phenyl) siloxymagnesium chloride, tris (2,3,4,5,6-pentamethylphenyl) siloxymagnesium chloride; tris (2-fluorophenyl) siloxymagnesium chloride, tris (3-fluorophenyl) siloxymagnesium chloride, tris ( 4-fluorophenyl) siloxymagnesium chloride, tris (2,2-difluorophenyl) siloxymagnesium chloride, tris (3,3-difluorophenyl) siloxymagnesium chloride, tris (2,3-difluorophenyl) siloxymagnesium chloride, tris ( 2,4-Difluorophenyl) siloximer Cesium chloride, tris (3,4-difluorophenyl) siloxymagnesium chloride, tris (2,4,6-trifluorophenyl) siloxymagnesium chloride, tris (2,3,4,5-tetrafluorophenyl) siloxymagnesium chloride, Tris (2,3,4,6-tetrafluorophenyl) siloxymagnesium chloride, Tris (2,3,5,6-tetrafluorophenyl) siloxymagnesium chloride, Tris (2,3,4,5,6-pentafluoro Phenyl) siloxymagnesium chloride; tris (2-methoxyphenyl) siloxymagnesium chloride, tris (3-methoxyphenyl) siloxymagnesium chloride, tris (4-methoxyphenyl) siloxymagnesium chloride, tris (2,2-dimethoxyphenyl) siloxymagnesium Chloride, Tris (3,3-Dimethoxy Phenyl) siloxymagnesium chloride, tris (2,3-dimethoxyphenyl) siloxymagnesium chloride, tris (2,4-dimethoxyphenyl) siloxymagnesium chloride, tris (3,4-dimethoxyphenyl) siloxymagnesium chloride, tris (2,4 , 6-Trimethoxyphenyl) siloxymagnesium chloride, tris (2,3,4,5-tetramethoxyphenyl) siloxymagnesium chloride, tris (2,3,4,6-tetramethoxyphenyl) siloxymagnesium chloride, tris (2 , 3,5,6-tetramethoxyphenyl) siloxymagnesium chloride, tris (2,3,4,5,6-pentamethoxyphenyl) siloxymagnesium chloride; dimethylphenylsiloxymagnesium chloride, methyldiphenylsiloxymagnesium chloride, diethylphenyl Loxymagnesium chloride, ethyldiphenylsiloxymagnesium chloride, di (tert-butyl) phenylsiloxymagnesium chloride, tert-butyldiphenylsiloxymagnesium chloride; dimethyl (methylphenyl) siloxymagnesium chloride, methyldi (methylphenyl) siloxymagnesium chloride, dimethyl (dimethyl Phenyl) siloxymagnesium chloride, methyldi (dimethylphenyl) siloxymagnesium chloride, dimethyl (trimethylphenyl) siloxymagnesium chloride, methyldi (trimethylphenyl) siloxymagnesium chloride, dimethyl (tetramethylphenyl) siloxymagnesium chloride, methyldi (tetramethylphenyl) siloxy Magnesium chloride, dimethyl (pentameth Ruphenyl) siloxymagnesium chloride, methyldi (pentamethylphenyl) siloxymagnesium chloride; dimethyl (fluorophenyl) siloxymagnesium chloride, methyldi (fluorophenyl) siloxymagnesium chloride, dimethyl (difluorophenyl) siloxymagnesium chloride, methyldi (difluorophenyl) siloxymagnesium Chloride, dimethyl (trifluorophenyl) siloxymagnesium chloride, methyldi (trifluorophenyl) siloxymagnesium chloride, dimethyl (tetrafluorophenyl) siloxymagnesium chloride, methyldi (tetrafluorophenyl) siloxymagnesium chloride, dimethyl (pentafluorophenyl) siloxymagnesium Chloride, methyldi ( Pentafluorophenyl) siloxymagnesium chloride; dimethyl (methoxyphenyl) siloxymagnesium chloride, methyldi (methoxyphenyl) siloxymagnesium chloride, dimethyl (dimethoxyphenyl) siloxymagnesium chloride, methyldi (dimethoxyphenyl) siloxymagnesium chloride, dimethyl (trimethoxyphenyl) Siloxymagnesium chloride, methyldi (trimethoxyphenyl) siloxymagnesium chloride, dimethyl (tetramethoxyphenyl) siloxymagnesium chloride, methyldi (tetramethoxyphenyl) siloxymagnesium chloride, dimethyl (pentamethoxyphenyl) siloxymagnesium chloride, methyldi (pentamethoxyphenyl) Siloxymagnesium chloride Dimethyl (trifluoromethylphenyl) siloxymagnesium chloride, methyldi (trifluoromethylphenyl) siloxymagnesium chloride, dimethyl (di (trifluoromethyl) phenyl) siloxymagnesium chloride, methyldi (di (trifluoromethyl) phenyl) siloxymagnesium chloride , Dimethyl (tri (trifluoromethyl) phenyl) siloxymagnesium chloride, methyldi (tri (trifluoromethyl) phenyl) siloxymagnesium chloride, dimethyl (tetra (trifluoromethyl) phenyl) siloxymagnesium chloride, methyldi (tetra (trifluoromethyl) ) Phenyl) siloxymagnesium chloride, dimethyl (penta (trifluoromethyl) phenyl) siloxymagnesium chloride , Methyldi (penta (trifluoromethyl) phenyl) siloxymagnesium chloride, di (tert-butyl) (trifluoromethylphenyl) siloxymagnesium chloride, methyldi (trifluoromethylphenyl) siloxymagnesium chloride, dimethyl (di (trifluoromethyl) ) Phenyl) siloxymagnesium chloride, methyldi (di (trifluoromethyl) phenyl) siloxymagnesium chloride, dimethyl (trifluoro (trifluoromethyl) phenyl) siloxymagnesium chloride, methyldi (tri (trifluoromethyl) phenyl) siloxymagnesium chloride, dimethyl (Tetra (trifluoromethyl) phenyl) siloxymagnesium chloride, methyldi (tetra (trifluoromethyl) phenyl) siloxymagnet Um chloride, dimethyl (penta (trifluoromethyl) phenyl) siloxymagnesium chloride, methyldi (penta (trifluoromethyl) phenyl) siloxymagnesium chloride; diphenylsilanedioxybis (magnesium chloride), di (methylphenyl) silanedioxybis ( Magnesium chloride), di (dimethylphenyl) silanedioxybis (magnesium chloride), di (trimethylphenyl) silanedioxybis (magnesium chloride), di (tetramethylphenyl) silanedioxybis (magnesium chloride), di (penta Methylphenyl) silanedioxybis (magnesium chloride); di (fluorophenyl) silanedioxybis (magnesium chloride), di (difluorophenyl) silanedioxide Bis (magnesium chloride), di (trifluorophenyl) silanedioxybis (magnesium chloride), di (tetrafluorophenyl) silanedioxybis (magnesium chloride), di (pentafluorophenyl) silanedioxybis (magnesium chloride) Di (methoxyphenyl) silanedioxybis (magnesium chloride), di (dimethoxyphenyl) silanedioxybis (magnesium chloride), di (trimethoxyphenyl) silanedioxybis (magnesium chloride), di (tetramethoxyphenyl) Silanedioxybis (magnesium chloride), di (pentamethoxyphenyl) silanedioxybis (magnesium chloride); di (trifluoromethylphenyl) silanedioxybis (magnesium chloride) , Di (di (trifluoromethyl) phenyl) silanedioxybis (magnesium chloride), di (tri (trifluoromethyl) phenyl) silanedioxybis (magnesium chloride), di (tetra (trifluoromethyl) phenyl) silane Examples include dioxybis (magnesium chloride) and di (penta (trifluoromethyl) phenyl) silanedioxybis (magnesium chloride).

The compound represented by the general formula (I ′) is preferably the above magnesium chloride compound, among which triphenylsiloxymagnesium chloride, tris (2-methylphenyl) siloxymagnesium chloride, tris (3-methylphenyl) siloxymagnesium chloride, Tris (4-methylphenyl) siloxymagnesium chloride, Tris (2-fluorophenyl) siloxymagnesium chloride, Tris (3-fluorophenyl) siloxymagnesium chloride, Tris (4-fluorophenyl) siloxymagnesium chloride, Tris (2-methoxyphenyl) ) Siloxymagnesium chloride, Tris (3-methoxyphenyl) siloxymagnesium chloride, Tris (4-methoxyphenyl) siloxymagnesium chloride, Dimethylphenylsiloxy Magnesium chloride, diphenylsilane dioxy bis (magnesium chloride) and the like are preferable.

The compound represented by the general formula (I ′) may be a coordination body, for example, a coordination body formed with the solvent according to the present invention. For example, when forming a coordination body with THF, it is estimated that the following dimeric coordination body is formed.

(In the formula, X, R ′ ₁ , R ′ ₂ and R ′ ₃ are the same as above.)

[Method for producing compound represented by general formula (I ′)]
The compound represented by the general formula (I ′) can be obtained, for example, by reacting a silanol compound represented by the following general formula (II ′) with a Grignard reagent in an appropriate solvent.

(Wherein R ′ ₁ to R ′ ₃ are the same as above)
Specific examples of the compound represented by the general formula (II ′) include those according to the specific examples of the compound represented by the general formula (I ′), and preferred compounds represented by the general formula (I ′) are also exemplified. The thing according to these preferable things is mentioned.

As the compound represented by the general formula (II ′), a commercially available product or a product produced by a method known per se may be used. As a method known per se, for example, after producing a compound represented by the following general formula (III ′) according to the method described in PaulPaD. Price et al, Dalton Tarnsactions, (2), 271-282, 2008 The compound is subjected to an oxidation method known per se.

(Wherein R ′ ₁ to R ′ ₃ are the same as above)
Specific examples of the compound represented by the general formula (III ′) include those according to the specific examples of the compound represented by the above general formula (I ′), and preferable compounds represented by the general formula (I ′) are also exemplified. The thing according to these preferable things is mentioned.

Examples of the Grignard reagent include a compound represented by RMgX (R represents a substituted alkyl group having 1 to 6 carbon atoms or a substituted phenyl group, and X is the same as above).
Examples of the alkyl group having 1 to 6 carbon atoms in R include the same as the alkyl group having 1 to 6 carbon atoms in R ₂ and R ₃ . Examples of the substituent of the alkyl group and the phenyl group in R include a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group, and specific examples thereof include the substituent of the aryl group in R ₁ . The same as the person who explained it.

The amount of the Grignard reagent used in the reaction of the silanol compound represented by the general formula (II ′) and the Grignard reagent is usually 0.5 to 2 mol relative to 1 mol of the compound represented by the general formula (II ′), The amount is preferably 0.5 to 1 mol.

The reaction temperature between the silanol compound represented by the general formula (II ′) and the Grignard reagent is usually −78 to 80 ° C., and the reaction time is usually 5 seconds to 5 hours. The reaction is preferably performed in an inert gas atmosphere such as argon or nitrogen, and more preferably performed in an argon atmosphere. As a solvent used in this case, any solvent may be used as long as at least one of the silanol compound represented by the general formula (II ′) or the Grignard reagent is dissolved, and a solvent capable of dissolving both is preferable. Specific examples include the same solvents as the above-mentioned present invention, among which diethyl ether, diglyme, triglyme, tetraglyme, tetrahydrofuran, 2-methyltetrahydrofuran, diisopropyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether. , Ether solvents such as triethylene glycol dimethyl ether, cyclopentyl methyl ether, t-butyl methyl ether, 1,4-dioxane, and the like, preferably tetrahydrofuran.
In addition, you may wash | clean the obtained reaction material with solvents, such as diisopropyl ether, after concentration drying.

Specifically, the compound represented by formula (I ′) is produced, for example, as follows.
That is, the silanol compound represented by the general formula (II ′) is dissolved in a solvent such as tetrahydrofuran under an argon gas atmosphere. Further, a tetrahydrofuran solution or the like in which 0.1 to 2 mol of phenylmagnesium chloride is dissolved is added dropwise with respect to 1 mol of the silanol compound, and the mixture is reacted for 5 seconds to 5 hours. If necessary, the reaction solution is concentrated and dried to obtain a solid, and the resulting solid is washed with a solvent such as diisopropyl ether and dried to produce the compound represented by the general formula (I ′). Is done.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 Preparation of Electrolytic Solution 1 (1) Synthesis of Magnesium Salt Under an argon gas atmosphere, 7.29 g (40 mmol) of benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) was added to tetrahydrofuran (THF) (manufactured by Wako Pure Chemical Industries, Ltd.). The solution was dissolved in 20 ml, and 20 ml (40 mmol) of a THF solution (manufactured by Tokyo Chemical Industry Co., Ltd.) of 2M phenylmagnesium chloride (PhMgCl) was added dropwise. After stirring for 4 hours, the crystals were collected by filtration and dried to obtain triphenylmethoxymagnesium chloride (Ph ₃ COMgCl).

(2) Preparation of electrolyte solution Under an argon gas atmosphere, 1.60 g (5 mmol) of triphenylmethoxymagnesium chloride (Ph ₃ COMgCl) was mixed with 20 ml of THF and heated to 50 ° C., then 0.67 g of aluminum chloride (AlCl ₃ ) (5 mmol) was added. After maintaining at 50 ° C. for 5 minutes, the solution was cooled and filtered to obtain an electrolytic solution 1 [triphenylmethoxymagnesium chloride-aluminum chloride / THF solution].

Example 2 Preparation of Electrolyte 2 Under an argon gas atmosphere, 1.60 g (5 mmol) of triphenylmethoxymagnesium chloride (Ph ₃ COMgCl) obtained in (1) of Example 1 was mixed with 20 ml of triglyme and heated to 50 ° C. After that, 0.17 g (1.25 mmol) of aluminum chloride (AlCl ₃ ) was added. After maintaining at 50 ° C. for 5 minutes, the solution was cooled and filtered to obtain an electrolytic solution 2 [triphenylmethoxymagnesium chloride-aluminum chloride / triglyme solution].

Example 3 Preparation of Electrolyte 3 Under an argon gas atmosphere, 1.60 g (5 mmol) of triphenylmethoxymagnesium chloride (Ph ₃ COMgCl) obtained in (1) of Example 1 was mixed with 20 ml of THF and heated to 35 ° C. Then, 0.48 g (5 mmol) of dimethylaluminum chloride (Me ₂ AlCl) (concentrated hexane solution manufactured by Kanto Chemical Co., Inc.) was added. After maintaining at 50 ° C. for 5 minutes, the mixture was cooled to obtain electrolytic solution 3 [triphenylmethoxymagnesium chloride-dimethylaluminum chloride / THF solution].

Example 4 Preparation of Electrolyte 4 (1) Synthesis of Magnesium Salt Under an argon gas atmosphere, a THF solution (manufactured by Tokyo Chemical Industry Co., Ltd.) in a THF solution (Tokyo Chemical Industry Co., Ltd.) with a concentration of 2M phenylmagnesium chloride (PhMgCl) was added. 30 ml of Kojun Pharmaceutical Co., Ltd.) was added, and 1.28 g (22 mmol) of acetone (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After stirring for 2 hours, the crystals were collected by filtration and dried to obtain dimethylphenylmethoxymagnesium chloride (Me ₂ PhCOMgCl).

(2) Preparation of electrolyte solution Under argon gas atmosphere, THF was mixed with 0.97 g (5 mmol) of dimethylphenylmethoxymagnesium chloride (Me ₂ PhCOMgCl), heated to 50 ° C., and then 0.17 g (1.25 mg) of aluminum chloride (AlCl ₃ ). mmol) was added. After maintaining at 50 ° C. for 5 minutes, the mixture was cooled to obtain electrolytic solution 4 [dimethylphenylmethoxymagnesium chloride-aluminum chloride / THF solution].

Example 5 Preparation of electrolyte solution 5 Under an argon gas atmosphere, 7.29 g (40 mmol) of benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 20 ml of THF (manufactured by Wako Pure Chemical Industries, Ltd.), and the concentration was 1M. 40 ml (40 mmol) of a THF solution (manufactured by Tokyo Chemical Industry Co., Ltd.) of allylmagnesium chloride ((C ₃ H ₅ ) MgCl) was added dropwise and stirred for 4 hours. To 12 ml (8 mmol) of the resulting solution, 0.17 g (2 mmol) of aluminum chloride (AlCl ₃ ) was added at room temperature and stirred for 1 hour, and the electrolyte solution 5 [1,1-diphenyl-1- (2-propenyl) was added. Methoxymagnesium chloride-aluminum chloride / THF solution] was obtained.

Example 6 Preparation of Electrolyte 6 Under Argon Gas Atmosphere, 4.36 g (20 mmol) of 4,4-difluorobenzophenone (Wako Pure Chemical Industries, Ltd.) was added to tetrahydrofuran (THF) (Wako Pure Chemical Industries, Ltd.) After dissolving in 15 ml, 10 ml (20 mmol) of a THF solution (manufactured by Tokyo Chemical Industry Co., Ltd.) of phenylmagnesium chloride (PhMgCl) at a concentration of 2M was added dropwise and stirred for 4 hours. After heating 6.8 ml (5 mmol) of the resulting solution to 40 ° C., 0.67 g (5 mmol) of aluminum chloride (AlCl ₃ ) was added and cooled, and the electrolyte 6 [1,1-di (4-fluorophenyl) 6 -1-phenylmethoxymagnesium chloride-aluminum chloride / THF solution] was obtained.

Comparative Example 1 Preparation of Comparative Electrolyte 1 Under Argon Gas Atmosphere, 2M Concentrated Ethyl Magnesium Chloride (EtMgCl) in THF (Tokyo Chemical Industry Co., Ltd.) 10ml (20mmol) and THF (Wako Pure Chemical Industries, Ltd.) 10 ml) was mixed, and 1.48 g (20 mmol) of tert-butanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. Thereafter, 0.44 g (3.3 mmol) of aluminum chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain Comparative Electrolytic Solution 1 [(tert-BuOMgCl) ₆ -AlCl ₃ / THF solution].

Comparative Example 2 Preparation of Comparative Electrolytic Solution 2 In an argon gas atmosphere, 0.5 g (5.3 mmol) of magnesium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 21 ml of THF (manufactured by Wako Pure Chemical Industries, Ltd.) Dimethylaluminum chloride (Me ₂ AlCl) (Concentrated hexane solution manufactured by Kanto Chemical Co., Inc.) 0.97 g (10.5 mmol) was added dropwise, and then tetrabutylammonium chloride (Bu ₄ NCl) (Tokyo Chemical Industry Co., Ltd.) 1.46 g (5.3 mmol) was added. After stirring at 60 ° C. for 2 days, the mixture was cooled to obtain Comparative Electrolytic Solution 2 [MgCl ₂ -Me ₂ AlCl—Bu ₄ NCl / THF solution].

Example 7 / Comparative Example 3 Cyclic Voltammetry (CV) Measurement of Various Electrolytic Solutions Using the electrolytic solutions 1 to 6, cyclic voltammetry (CV) measurement was performed (Example 7). Similarly, CV measurement was performed using Comparative Electrolytic Solutions 1 and 2 (Comparative Example 3).
Specifically, the CV measurement was performed as follows. That is, using a 3-pole beaker cell, platinum electrode (diameter 3 mm; manufactured by BAS) as working electrode, Mg rod (diameter 1.6 mm; manufactured by Niraco) as counter electrode, and Mg rod (diameter 1.6 mm; Niraco) as reference electrode Used). 2 ml of the electrolyte was added to the beaker, and measurements were made in the range of -1.5 to 3.5 V at room temperature (25 ° C) at a sweep rate of 5 mV / s. For the measurement, an electrochemical measurement system (manufactured by BioLogic) was used.

The results of the oxidative decomposition potential (10th cycle) of each electrolytic solution are shown in the following table.
The results of the 10th cycle of the electrolytic solution 1 are shown in FIG. 1, the results of the 10th and 40th cycles of the electrolytic solution 2 are shown in FIGS. 2 and 3, respectively, and the results of the 10th cycle of the comparative

electrolytic solutions

1 and 2 are shown. Are shown in FIGS. The horizontal axis in the figure represents the potential of the working electrode based on the potential of the reference electrode, and the vertical axis (mA / cm ² ) represents the current obtained by dividing the current value observed at each potential by the surface area of the working electrode. Represents density.

From the results of Table 1, it was found that the electrolytic solution of the present invention has an oxidative decomposition potential of +2.8 V to +3.4 V, and can be used at a high voltage equal to or higher than that of the conventional method. Furthermore, from the results of FIG. 3, it was found that the electrolytic solution 2 can be used stably without deterioration even after dissolution and precipitation of magnesium 40 times.

On the other hand, Comparative Electrolytic Solution 2 [(t-BuOMgCl) ₆ -AlCl ₃ in THF] is an electrolytic solution described in J. Mater. Chem. A, 2014, 2, 581-584 (Non-patent Document 3). . As a result of CV measurement using the electrolytic solution, it was confirmed that the oxidative decomposition potential was +2.4 V almost as per the literature value.

Experimental Example 1 Confirmation of Copper Plate Surface by Scanning Electron Microscope (SEM) It was confirmed by SEM (manufactured by Hitachi High-Technologies Corporation) whether the current in cyclic voltammetry (CV) measurement of electrolyte solution 1 was a result of Mg dissolution and precipitation.
Specifically, using a 3-pole beaker cell, the working electrode is a copper plate (thickness 0.1 mm; manufactured by Nilaco), the counter electrode is an Mg rod (diameter 1.6 mm; manufactured by Nilaco), and the reference electrode is an Mg rod (diameter). 1.6 mm; manufactured by Niraco) was used. 2 ml of the electrolyte solution of Example 1 was added to the beaker, and magnesium was deposited on the copper plate at room temperature (25 ° C.) at a current value of 0.1 mA for 5 hours. In this experiment, an electrochemical measurement system (manufactured by BioLogic) was used.

After the precipitation, the copper plate surface was confirmed by SEM, and as a result, the deposition of magnesium was confirmed. In addition, elemental analysis of magnesium, aluminum, copper, chlorine, carbon, and oxygen was performed by EDS (energy dispersive X-ray analysis), and it was also confirmed that the precipitate was magnesium.

Example 8 Preparation of Electrolyte 7 (1) Synthesis of Magnesium Salt Under an argon gas atmosphere, 11.1 g (40 mmol) of triphenylsilanol (Tokyo Chemical Industry Co., Ltd.) was added to tetrahydrofuran (THF) (Wako Pure Chemical Industries, Ltd.). 20 ml (40 mmol) of a THF solution (manufactured by Tokyo Chemical Industry Co., Ltd.) with a concentration of 2M phenylmagnesium chloride (PhMgCl) was added dropwise and stirred for 1 hour. Thereafter, the solution was concentrated and dried, and the resulting powder was washed with 70 ml of diisopropyl ether (manufactured by Wako Pure Chemical Industries, Ltd.). The powder was collected by filtration and dried to obtain triphenylsiloxymagnesium chloride (Ph ₃ SiOMgCl).

The measurement results of ¹ H-NMR are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.25-7.80 (m, 15H)

(2) Preparation of electrolyte solution Under argon gas atmosphere, triphenylsiloxymagnesium chloride (Ph ₃ SiOMgCl) 3.35 g (10 mmol) was mixed with 40 ml of THF (manufactured by Wako Pure Chemical Industries, Ltd.) and heated to 50 ° C. Then, 1.33 g (10 mmol) of aluminum chloride (AlCl ₃ ) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After maintaining at 50 ° C. for 10 minutes, the mixture was cooled and filtered after 1 week to obtain an electrolytic solution 7 [triphenylsiloxymagnesium chloride-aluminum chloride / THF solution].

Example 9 Preparation of Electrolyte 8 Under an argon gas atmosphere, THF (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 0.84 g (2.5 mmol) of triphenylsiloxymagnesium chloride (Ph ₃ SiOMgCl) obtained in Example 8 (1). 10 ml was mixed, and 0.5 ml (0.5 mmol) of a solution of trichloroborane (BCl ₃ ) in dichloromethane (CH ₂ Cl ₂ ) (made by Wako Pure Chemical Industries, Ltd.) having a concentration of 1M was added dropwise at room temperature. After heating and maintaining at 50 ° C. for 10 minutes, the mixture was concentrated and 10 ml of tetrahydrofuran (THF) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After 8 ml (2 mmol) of the obtained solution was heated to 50 ° C., 0.21 g (1.6 mmol) of aluminum chloride (AlCl ₃ ) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After maintaining at 50 ° C. for 10 minutes, the mixture was cooled to obtain an electrolytic solution 8 [triphenylsiloxymagnesium chloride-aluminum chloride-trichloroborane / THF solution].

Example 10 Preparation of Electrolyte 9 Triglyme (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 0.84 g (2.5 mmol) of triphenylsiloxymagnesium chloride (Ph ₃ SiOMgCl) obtained in Example 8 (1) under an argon gas atmosphere. After mixing 10 ml and heating to 50 ° C., 0.33 g (2.5 mmol) of aluminum chloride (AlCl ₃ ) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After maintaining at 50 ° C. for 10 minutes, the mixture was cooled and filtered after 1 week to obtain an electrolytic solution 9 [triphenylsiloxymagnesium chloride-aluminum chloride / triglyme solution].

Example 11 Preparation of Electrolytic Solution 10 (1) Tris (4-methylphenyl) silanol A THF solution of 1.0-methylphenylmagnesium bromide (1.0 M, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 1000 mL flask under a nitrogen atmosphere. mL (288 mmol) was added. Thereafter, a solution obtained by dissolving 12.2 g (90 mmol) of trichlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) in 302 mL of THF was added dropwise over 1 hour while keeping the temperature of the solution in the flask at 35 ° C. or lower. After completion of dropping, the mixture was further stirred at room temperature for 2 hours to be reacted. After completion of the reaction, 45 mL of hydrochloric acid (1.0 M) was added dropwise for neutralization. Subsequently, 450 mL of diisopropyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) was added to separate the layers. Further, the organic layer was washed with 45 mL of hydrochloric acid (1.0 M) and separated. The organic layer was dried by adding 30 g of magnesium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.). After filtering the magnesium sulfate, the filtrate was concentrated under reduced pressure to obtain a crude product of tris (4-methylphenyl) silane. Further, the crude product was dissolved in 50 mL of diisopropyl ether and 50 mL of ethanol, and concentrated under reduced pressure to crystallize. The precipitated white solid was filtered and washed with ethanol (60 mL). The obtained solid was dried under reduced pressure to obtain 20.44 g (67.6 mmol, yield 75%, white solid) of tris (4-methylphenyl) silane.
¹ H-NMR (400 MHz, CDCl ₃ ) 2.36 (s, 9H, Me), 5.41 (s, 1H, SiH), 7.18 (d, 6H, J = 8.2 Hz, Ar), 7.46 (d, 6H, J = 8.2 Hz, Ar)

Next, 6.05 g (20 mmol) of the obtained tris (4-methylphenyl) silane and 375 mL of THF were added to a 1000 mL flask under a nitrogen atmosphere. Furthermore, 3.32 g (21 mmol) of potassium permanganate (manufactured by Wako Pure Chemical Industries, Ltd.) and ion-exchanged water (3.8 ml) were added. The mixture was stirred and reacted at 60 ° C. for 13 hours while applying ultrasonic waves to the flask using an ultrasonic cleaner (US-2, manufactured by ASONE). After completion of the reaction, the mixed solution was passed through 60 g of silica gel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.), and the by-product manganese oxide was filtered. The filtrate was concentrated under reduced pressure to obtain a crude product of tris (4-methylphenyl) silanol. The obtained crude product was dissolved in 30 mL of dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.) and 60 mL of n-hexane (Wako Pure Chemical Industries, Ltd.), and concentrated under reduced pressure to crystallize. The precipitated white solid was filtered and washed with n-hexane (10 mL). The obtained solid was dried under reduced pressure to obtain 3.1 g (9.58 mmol, yield 48%, white solid) of tris (4-methylphenyl) silanol.
¹ H-NMR (400 MHz, C ₆ D ₆ ) (ppm): 1.89 (s, 1H, SiOH), 2.10 (s, 9H, Me), 7.06 (d, 6H, J = 8.2 Hz, Ar), 7.68 (d, 6H, J = 8.2 Hz, Ar)

(2) Synthesis of magnesium salt Under an argon gas atmosphere, 2.55 g (8 mmol) of the obtained tris (4-methylphenyl) silanol was dissolved in 12 ml of tetrahydrofuran (THF) (manufactured by Wako Pure Chemical Industries, Ltd.) to a concentration of 2M. 3.8 ml (7.6 mmol) of phenylmagnesium chloride (PhMgCl) in THF (Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred for 1 hour. Thereafter, the solution was concentrated and dried, and the resulting powder was washed with 30 ml of diisopropyl ether (manufactured by Wako Pure Chemical Industries, Ltd.). The powder was collected by filtration and dried to obtain tris (4-methylphenyl) siloxymagnesium chloride ((4-Me-C ₆ H ₄ ) ₃ SiOMgCl).

The measurement results of ¹ H-NMR are shown below.
¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm): 2.33 (s, 9H) 7.14-7.17 (d, 6H, J = 7.0Hz) 7.58-7.61 (d, 6H, J = 7.0Hz)

(3) Preparation of electrolyte solution Under argon gas atmosphere, tris (4-methylphenyl) siloxymagnesium chloride ((4-Me-C ₆ H ₄ ) ₃ SiOMgCl) 0.94 g (2.5 mmol) was mixed with THF (Wako Pure Chemical Industries, Ltd. ( 10 ml) was mixed and heated to 50 ° C., and 0.33 g (2.5 mmol) of aluminum chloride (AlCl ₃ ) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The mixture was maintained at 50 ° C. for 10 minutes and then cooled to obtain an electrolytic solution 10 [Tris (4-methylphenyl) siloxymagnesium chloride-aluminum chloride / THF solution].

Example 12 Preparation of Electrolytic Solution 11 (1) Synthesis of Tris (4-fluoro) silanol A THF solution of 1.0-fluorophenylmagnesium bromide (1.0 M, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 1000 mL flask under a nitrogen atmosphere. 288 mL (288 mmol) was added. Thereafter, a solution obtained by dissolving 12.2 g (90 mmol) of trichlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) in 302 mL of THF was added dropwise over 1 hour while keeping the temperature of the solution in the flask at 35 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours to be reacted. After completion of the reaction, 45 mL of hydrochloric acid (1.0 M) was added dropwise for neutralization. Next, 450 mL of diisopropyl ether was added to separate the layers. Further, the organic layer was washed with 45 mL of hydrochloric acid (1.0 M) and separated. To the obtained organic layer, 30 g of magnesium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dried. After filtering the magnesium sulfate, the filtrate was concentrated under reduced pressure to obtain a crude product of tris (4-fluorophenyl) silane. Further, 30 mL of n-pentane (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the crude product, and only the oiled-out colored components were removed with a dropper. The remaining solution was concentrated under reduced pressure. The precipitated solid was filtered and washed with 30 mL of ethanol. The obtained white solid was dried under reduced pressure to obtain 22.68 g (72.1 mmol, yield 80%, white solid) of tris (4-fluorophenyl) silane.
¹ H-NMR (400 MHz, CDCl ₃ ) 5.44 (s, 1H, SiH), 7.05-7.11 (m, 6H, Ar), 7.47-7.52 (m, 6H, Ar)

Next, 6.29 g (20 mmol) of the obtained tris (4-fluorophenyl) silane and 375 mL of THF were added to a 1000 mL flask under a nitrogen atmosphere. Furthermore, 3.32 g (21 mmol) of potassium permanganate (manufactured by Wako Pure Chemical Industries, Ltd.) and ion-exchanged water (3.8 ml) were added. While applying ultrasonic waves to the flask using an ultrasonic cleaner (US-2, manufactured by ASONE Co., Ltd.), the mixture was stirred and reacted for 4 hours while maintaining a temperature below room temperature. After completion of the reaction, the mixed solution was passed through 60 g of silica gel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.), and the by-product manganese oxide was filtered. The filtrate was concentrated under reduced pressure to obtain a crude product of tris (4-fluorophenyl) silanol. After purification with a silica gel column (developing solvent: ethyl acetate / n-hexane = 1/9 (both ethyl acetate and n-hexane are manufactured by Wako Pure Chemical Industries, Ltd.)), the residue is dried under reduced pressure and tris (4-fluorophenyl) 2.55 g (7.72 mmol, yield 39%, white solid) of silanol was obtained.
1H-NMR (400 MHz, CDCl3) δ: 2.50 (s, 1H, SiOH), 7.07-7.14 (m, 6H, Ar), 7.54-7.60 (m, 6H, Ar)

(2) Synthesis of magnesium salt Under an argon gas atmosphere, 2.15 g (6.5 mmol) of the obtained tris (4-fluorophenyl) silanol was dissolved in 19.5 ml of tetrahydrofuran (THF) (manufactured by Wako Pure Chemical Industries, Ltd.) 3.1 ml (6.2 mmol) of a THF solution (manufactured by Tokyo Chemical Industry Co., Ltd.) of phenylmagnesium chloride (PhMgCl) having a concentration of 2M at −78 degrees was added dropwise and stirred for 1 hour. To the oil produced by concentrating and drying the solution, 50 ml of hexane (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 ml of diisopropyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) were added to produce a powder. The powder was collected by filtration and dried to obtain tris (4-fluorophenyl) siloxymagnesium chloride ((4-F-C6H4) 3SiOMgCl).

The measurement results of 1H-NMR are shown below.
1H-NMR (400 MHz, CDCl3) δ (ppm): 7.06-7.11 (t, 6H, J = 8.8Hz) 7.64-7.68 (t, 6H, J = 7.0Hz)

(3) Preparation of electrolyte solution Under argon gas atmosphere, tris (4-fluorophenyl) siloxymagnesium chloride ((4-F-C6H4) 3SiOMgCl) 0.86 g (2.2 mmol) to THF (manufactured by Wako Pure Chemical Industries, Ltd.) After mixing 8.8 ml and heating to 50 ° C., 0.29 g (2.2 mmol) of aluminum chloride (AlCl 3) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The mixture was maintained at 50 ° C. for 10 minutes and then cooled to obtain an electrolytic solution 11 [Tris (4-fluorophenyl) siloxymagnesium chloride-aluminum chloride / THF solution].

Example 13 Preparation of Electrolytic Solution 12 (1) Synthesis of Tris (3,5-dimethoxyphenyl) silanol In a 2000 mL flask, 6.36 g (0.262 mol) of Mg scraped (Wako Pure Chemical Industries, Ltd.) and iodine (Wako Pure Chemical Industries, Ltd.) 10 mg) was added and dried under reduced pressure for 1 hour. Furthermore, 222 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added under a nitrogen atmosphere. Next, a solution of 52.1 g (0.240 mol) of 1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) in 274 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1.5 hours. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Furthermore, a solution of 10.2 g (0.075 mol) of trichlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 252 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour while keeping the temperature in the flask at 35 ° C. or lower. did. After completion of dropping, the reaction was allowed to proceed at room temperature for 1 hour. After completion of the reaction, 45 mL of hydrochloric acid (1.0 M, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to neutralize, and 450 mL of diisopropyl ether (produced by Wako Pure Chemical Industries, Ltd.) was added for liquid separation. Further, the organic layer was washed with 45 mL of hydrochloric acid (1.0 M, manufactured by Wako Pure Chemical Industries, Ltd.) and separated. The organic layer was dried by adding 30 g of magnesium sulfate (Wako Pure Chemical Industries, Ltd.). Thereafter, magnesium sulfate was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product of tris (3,5-dimethoxyphenyl) silane. The obtained crude product was dissolved in 50 mL of diisopropyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 ml of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), concentrated under reduced pressure, and crystallized. The precipitated white solid was filtered and washed with ethanol (30 mL). The obtained solid was dried under reduced pressure to obtain 28.7 g (65.0 mmol, yield 87%, white solid) of tris (3,5-dimethoxyphenyl) silane.
1H-NMR (400 MHz, CDCl3) δ (ppm): 3.75 (s, 18H, OMe), 5.34 (s, 1H, SiH), 6.50 (t, 3H, J = 2.4 Hz, Ar), 6.71 (d, 6H, J = 2.4 Hz, Ar)

Next, 8.81 g (20 mmol) of the obtained tris (3,5-dimethoxyphenyl) silane and 375 mL of THF were added to a 1000 mL flask under a nitrogen atmosphere. Furthermore, 3.32 g (21 mmol) of potassium permanganate (manufactured by Wako Pure Chemical Industries, Ltd.) and ion-exchanged water (3.8 ml) were added. While applying ultrasonic waves to the flask using an ultrasonic cleaner (US-2, manufactured by ASONE Co., Ltd.), the mixture was stirred and reacted for 1 hour while maintaining a temperature below room temperature. After completion of the reaction, the mixed solution was passed through 60 g of silica gel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.), and the by-product manganese oxide was filtered. The filtrate was concentrated under reduced pressure to obtain a crude product of tris (3,5-dimethoxyphenyl) silanol. The obtained crude product was dissolved in 20 mL of dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 mL of n-hexane (Wako Pure Chemical Industries, Ltd.), concentrated and crystallized. The precipitated white solid was filtered and washed with n-hexane (30 mL). The obtained solid was dried under reduced pressure to obtain 7.68 g (16.8 mmol, 84% yield, white solid) of tris (3,5-dimethoxyphenyl) silanol.
1H-NMR (400 MHz, CDCl3) δ (ppm): 2.46 (s, 1H, SiOH), 3.75 (s, 18H, OMe), 6.52 (t, 3H, J = 2.4 Hz, Ar), 6.76 (d, 6H, J = 2.4 Hz, Ar)

(2) Synthesis of magnesium salt Under an argon gas atmosphere, 3.65 g (8 mmol) of the obtained tris (3,5-dimethoxyphenyl) silanol was dissolved in 30 ml of THF, and a THF solution of phenylmagnesium chloride (PhMgCl) at a concentration of 2M ( 3.8 ml (7.6 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added dropwise and stirred for 1 hour. Thereafter, the solution was concentrated and dried, and the resulting powder was washed with 36.5 ml of diisopropyl ether (manufactured by Wako Pure Chemical Industries, Ltd.). The powder was collected by filtration and dried to obtain tris (3,5-dimethoxyphenyl) siloxymagnesium chloride ((3,5- (MeO) 2-C6H3) 3SiOMgCl).

The measurement results of 1H-NMR are shown below.
1H-NMR (400MHz, CDCl3) δ (ppm): 3.75 (s, 18H) 6.44-6.48 (t, 3H, J = 2.4Hz) 6.80-6.91 (d, 6H, J = 2.4Hz)

(3) Preparation of electrolyte solution Under argon gas atmosphere, tris (3,5-dimethoxyphenyl) siloxymagnesium chloride ((3,5- (MeO) 2-C6H3) 3SiOMgCl) 1.29 g (2.5 mmol) was mixed with 10 ml of THF. After heating to 50 ° C., 0.33 g (2.5 mmol) of aluminum chloride (AlCl 3) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The mixture was maintained at 50 ° C. for 10 minutes and then cooled to obtain an electrolytic solution 12 [Tris (3,5-dimethoxyphenyl) siloxymagnesium chloride-aluminum chloride / THF solution].

Example 14 Preparation of Electrolysis 13 (1) Synthesis of Magnesium Salt Under an argon gas atmosphere, 4.57 g (30 mmol) of dimethylphenylsilanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added to tetrahydrofuran (THF) (Wako Pure Chemical Industries, Ltd.). 15 ml (30 mmol) of a THF solution of phenylmagnesium chloride (PhMgCl) having a concentration of 2M (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred for 1 hour. 30 ml of hexane (manufactured by Wako Pure Chemical Industries, Ltd.) and 85 ml of t-butyl methyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) were added to the oil produced by concentrating and drying the solution to produce a powder. The powder was collected by filtration and dried to obtain dimethylphenylsiloxymagnesium chloride (Me2PhSiOMgCl).

The measurement results of 1H-NMR are shown below.
1H-NMR (400 MHz, CDCl3) δ (ppm): 0.20-0.60 (m, 6H) 7.20-7.40 (m, 3H) 7.50-7.70 (m, 2H)

(2) Preparation of electrolyte solution Under an argon gas atmosphere, 20 ml of THF (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed with 1.06 g (5 mmol) of dimethylphenylsiloxymagnesium chloride (Me ₂ PhSiOMgCl) and heated to 50 ° C. Then, 0.67 g (5 mmol) of aluminum chloride (AlCl ₃ ) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The mixture was maintained at 50 ° C. for 10 minutes and then cooled to obtain an electrolytic solution 13 [dimethylphenylsiloxymagnesium chloride-aluminum chloride / THF solution].

Example 15 Preparation of Electrolytic Solution 14 (1) Synthesis of Magnesium Salt Under an argon gas atmosphere, diphenylsilanediol (Tokyo Chemical Industry Co., Ltd.) 8.65 g (40 mmol) was added to tetrahydrofuran (THF) (Wako Pure Chemical Industries, Ltd.) The product was dissolved in 20 ml, and 40 ml (80 mmol) of a THF solution (manufactured by Tokyo Chemical Industry Co., Ltd.) of phenylmagnesium chloride (PhMgCl) at a concentration of 2M was added dropwise and stirred for 1 hour. Thereafter, the solution was concentrated and dried, and the resulting powder was washed with 50 ml of diisopropyl ether (manufactured by Wako Pure Chemical Industries, Ltd.). The powder was collected by filtration and dried to obtain diphenylsilanedioxybis (magnesium chloride) (Ph ₂ Si (OMgCl) ₂ ).

The measurement results of ¹ H-NMR are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 6.90-8.00 (m, 10H)

(2) Preparation of electrolyte solution Under argon gas atmosphere, diphenylsilanedioxybis (magnesium chloride) (Ph ₂ Si (OMgCl) ₂ ) 0.83 g (2.5 mmol) was added 20 ml of THF (manufactured by Wako Pure Chemical Industries, Ltd.) After mixing and heating to 50 ° C., 0.67 g (5 mmol) of aluminum chloride (AlCl ₃ ) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The mixture was maintained at 50 ° C. for 10 minutes and then cooled to obtain an electrolytic solution 14 [diphenylsilanedioxybis (magnesium chloride) -aluminum chloride / THF solution].

Comparative Example 4 Preparation of Comparative Electrolytic Solution 3 Trimethylsilanol (Me ₃ SiOH) (5 mmol (10 mmol) in 2M concentration of ethyl magnesium chloride (EtMgCl) in THF (Tokyo Chemical Industry Co., Ltd.) under an argon gas atmosphere ( 0.90 g (10 mmol) (Aldrich) was added dropwise and air-cooled. At room temperature, 0.22 g (1.67 mmol) of aluminum chloride (AlCl ₃ ) (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred for 1 hour. Comparative electrolyte 3 [(Me ₃ SiOMgCl) ₆ -AlCl ₃ / THF Solution] was obtained.

Example 16 Preparation of Electrolytic Solution 15 (1) Synthesis of Magnesium Salt Under an argon gas atmosphere, 5.53 g (20 mmol) of triphenylsilanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to tetrahydrofuran (THF) (Wako Pure Chemical Industries, Ltd.). The product was dissolved in 20 ml, and 10 ml (10 mmol) of a THF solution of phenylmagnesium bromide (PhMgBr) having a concentration of 1M (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and reacted for 1 hour. Thereafter, the solution was concentrated and dried, and the resulting oil was pulverized with 40 ml of diisopropyl ether (manufactured by Wako Pure Chemical Industries, Ltd.). The powder was collected by filtration and dried to obtain triphenylsiloxymagnesium bromide (Ph ₃ SiOMgBr).

The measurement results of ¹ H-NMR are shown below.
¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm): 6.95-7.90 (m, 15H)

(2) Preparation of electrolyte solution Under argon gas atmosphere, triphenylsiloxymagnesium bromide (Ph ₃ SiOMgBr)) 0.95 g was mixed with 10 ml of THF (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 50 ° C., and then chlorinated. 0.33 g (2.5 mmol) of aluminum (AlCl ₃ ) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After maintaining at 50 ° C. for 10 minutes, the mixture was cooled and filtered to obtain an electrolytic solution 15 [triphenylsiloxymagnesium bromide-aluminum chloride / THF solution].

Example 17 / Comparative Example 5 Cyclic Voltammetry (CV) Measurement of Various Electrolytic Solutions Using the electrolytic solutions 7 to 15, cyclic voltammetry (CV) measurement was performed in the same manner as in Example 7 (Example 17). . Similarly, CV measurement was performed in the same manner as in Example 7 using the comparative electrolytic solution 3 (Comparative Example 5).

The results of the oxidative decomposition potential of each electrolytic solution are shown in Table 2 below.
Moreover, the result of the 10th cycle of the electrolytic solution 7 is shown in FIG. 6, and the result of the 10th cycle of the comparative electrolytic solution 3 is shown in FIG. The horizontal axis in the figure represents the potential of the working electrode based on the potential of the reference electrode, and the vertical axis (mA / cm ² ) represents the current obtained by dividing the current value observed at each potential by the surface area of the working electrode. Represents density.

From the results in Table 2, the electrolytic solution of the present invention using a silicon compound has an oxidative decomposition potential of +2.8 V to +3.2 V, which is higher than the conventional method, and can be used at a high voltage. I found it possible.
Moreover, about the electrolyte solution 7, CV measurement was performed using the thing after 1 month preservation | save, and it also confirmed that the oxidative decomposition potential of + 3.2V was shown. Therefore, it turned out that the electrolyte solution of this application is excellent in storage stability.

Claims

Electrolytic solution for magnesium battery comprising a compound represented by the following general formula (I), Lewis acid and solvent:

(In the formula, Y represents a carbon atom or a silicon atom, X represents a chlorine atom or a bromine atom,
R 1 represents a halogeno group, an alkyl group, a halogenoalkyl group, or an aryl group having 6 to 10 carbon atoms which may have an alkoxy group as a substituent,
R 2 and R 3 each independently have a magnesium chlorideoxy group (—OMgCl); a magnesium bromideoxy group (—OMgBr); an alkenyl group having 1 to 6 carbon atoms; a halogeno group or an alkoxy group as a substituent. An optionally substituted alkyl group having 1 to 6 carbon atoms; or an aryl group having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent. ).
The electrolyte solution for magnesium batteries according to claim 1, wherein the Lewis acid contains beryllium, boron, aluminum, silicon, tin, titanium, chromium, iron, or cobalt as an element.
The electrolyte solution for magnesium batteries according to claim 1, wherein the Lewis acid contains aluminum as an element.
The electrolyte solution for magnesium batteries according to claim 1, wherein the Lewis acid is aluminum chloride.
R 1 in the magnesium compound is an aryl group having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, or an alkoxy group as a substituent;
R 2 and R 3 are each independently a magnesium chlorideoxy group (—OMgCl); an alkenyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms; or a halogeno group, an alkyl group, or an alkoxy group The electrolytic solution for magnesium battery according to claim 1, which is an aryl group having 6 to 10 carbon atoms which may have as a substituent.
R 1 in the magnesium compound is a phenyl group optionally having a halogeno group, an alkyl group, or an alkoxy group as a substituent,
R 2 and R 3 are each independently —OMgCl; an alkenyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms; or a phenyl group optionally having an alkyl group as a substituent. The electrolyte solution for magnesium batteries according to claim 1.
The electrolyte solution for magnesium batteries according to claim 1, wherein X in the magnesium compound is a chlorine atom.
The electrolyte for magnesium batteries according to claim 1, wherein the solvent is an ether, halogenated hydrocarbon, carbonate, or nitrile.
An electrochemical device comprising the electrolytic solution according to any one of claims 1 to 8, a positive electrode, and a negative electrode.
Compound represented by the following general formula (I ′):

(In the formula, X represents a chlorine atom or a bromine atom, and R ′ 1 is an aryl group having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent. Represents
R ′ 2 and R ′ 3 each independently represents a magnesium chlorideoxy group (—OMgCl); a magnesium bromideoxy group (—OMgBr); an alkenyl group having 1 to 6 carbon atoms; a halogeno group or an alkoxy group as a substituent. An alkyl group having 1 to 6 carbon atoms which may have; or an aryl group having 6 to 10 carbon atoms which may have a halogeno group, an alkyl group, a halogenoalkyl group or an alkoxy group as a substituent. . ).